8-hydroxyquinoline disazo-dyestuffs



2,743,266 8-HYDROXYQU1NOLINE DISAZO-DYESTUFFS Hans Liechti, Riehen, and Karl Menzi and Fritz Oesterlein, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm i No Drawing. Application March 3, 1952 Serial No. 274,654

Claims priority, application Switzerland March 8, 1951 I Claim. (Cl. 260-155) This invention provides new. disazo-dyestuifs. These dyestuifs, in the form of their free acids, correspond to the general formula in which R1 represents a benzene radical containing a nitrogen atom an aryl radical containing a sulfonic acid group.

Such compounds can be made by sulfonating the corresponding ortho-hydroxy-nitro-compounds free from sulfonic acid groups, and reducing the nitro group in the resulting product to the amino group, or by condensing the appropriate l-hydroxy-Z-uitrobenzene carboxylic acids or their halides with arylarnines containing sulfonic acid groups, and reducing the nitro group in the.re,sult ing product to the amino group.

A number of l-hydroxy-Z-aminobenzene carboxylic acid amides are known (see, for example, U. S. Patent pounds of the amino-monoazo-dyestulfs,

carboxylic acid amide group and in ortho-position to the azo linkage a hydroxyl group, and R2 represents the radical of an 8-hydroxyquinoline. These disazo-dyestufls are made in accordance with the invention by coupling a diazo compound of anamino-monoazo-dyestufi ofthe general formula R1N=N HOsS-- Nn-oo -ONH,

in which R1 represents a benzene radical containing a carboxylic acid amide group and in orthoposition to the Among the S-hydroxyquinolines, which are to he coupled by the process of the invention with the diazo com- 8-hydroxyquinoline itself is of special value. However, there may be used substituted S-hydroxyquinolines, such, for example, as S-chloro-S-hydroxyquinoline or 8-hydroxyquino line-7-sulfonic acid. I

The diazotization of the amino-monoazo-dyestufl's of the Formula 2 can be carried out by the ordinary known methods, for example, with the aid of hydrochloric acid and sodium nitrite. The coupling of the diazotized amino-monoazo-dyestuffs with the S-hydroxyquinolines is advantageously carried out in an alkaline medium for example a medium rendered alkaline with an alkali carbonate or an alkali hydroxide. When the 8-hydroxy quinolines are free from groups imparting solubility such as sulfonic acid groups, it is generally desirable to bring them into a form well suited for coupling by first dissolving them in water in the form of the hydrochloride, mixing the resulting solution with the diazotization mixture and then adding an excessof alkali.

The disazo dyestufls of this invention, and correspond ing to the foregoing general Formula 1, especially those which correspond to the formula As ortho-hydroxy-diazo benzene carboxylic acid amides there come into consideratiomfor example, diazo compounds of l-hydroxy-Z-aminobenzene carboxylic acid amides, which contain the carboxylic acid amide group in the 5- or 6-position or advantageously in the 4-position. The benzene nucleus may, if desired, contain further substituents, for example a halogen atomsuch as bromine or chlorine, or a methyl or nitro group. These l-hydroxy- Z-aminobenzene carboxylic acid amides can be made in known manner from the appropriate 1-hydroxy-2-nitrobenzene carboxylic acids or more especially from the halides of these acids by condensation with ammonia, or a secondary or advantageously a primary amine, followed J by reduction of the. nitro group,

For the condensationthere may be used, for. example, the following amines: Ethylamine, diethylamine, butylamine, monoethanolarnine, benzylamine, cyclohexylamine, Z-aminothiazole, 'l-aminonaphthalene or 2-aminonaphthalene. .Of special interest are aromatic amines of the benzene series, for example, alkylphenylamines such as N-methylaminobenzene, but especially primary amines of this kind such as aminobenzene, l'chloro-l-aminoben- ,zene, Z-methoxy-l-aminobenzene, 4-ethyl-l-aminobenzene or 4-ethoxy-1-amindbenzene. There may also benused .1-hydroxy-2 -aminobenzene carboxylic acid amides containing sulfonic .acidlgroups,

'for example, those containing as a substituent at the in which Y represents a carboxylic acid amide group bound to the benzene nucleus I by its -CO-- group, are suitable for dyeing or printing a very wide vaiiety of materials, for example animal fibers such as wool, silk and leather, but especially for dyeing and. printing cellulose materials such as cotton, linen, and artificial silk and staple fibers of regenerated cellulose. The dyestuils may be converted in substance, in the dyebath or on the fiber into complex metal compounds, for example, copper, chromium, iron, nickel or cobalt compounds. Conversion into such complex metal compounds is carried out by methods in themselves known in an acid, neutral or alkaline medium, under atmospheric or superatrnos pheric pressure, with or without additions such as salts of inorganic or organic acids such as tartaric acid, acidbinding agents or agents capable of favoring the .forma tion of complexes, such as pyridine. It is especially useful to prepare the metal compounds, more particularly the copper compounds, on a substratum when the metal free dyestuffs exhibit too low a degree of .aflinity and/or when the metalliferous dyestuiis are still sufiiciently soluble. Thus, in the case of dyestuffs yielding sparingly soluble metal compounds,'they may be treated, fore-re ample, advantageously on the fiber or partially ,on the fiber andv partially in the dyebath by known methods with agents yielding metal. It is of advantage to use,

for example, the process of U. S. Patent No. 2,148,659 in which first the dyeing and then the treatment with an agent yielding metal are carried out in the same bath. As agents yielding metal there come into consideration in this connection especially those which are stable 'to-- wards alkaline solutions, such as complex copper tartrates and the like.

In many cases especially valuable dyeings can be produced by using the process in which the dyeings or prints produced with the metal-free dyestuffs are after-treated with aqueous solutions which contain a basic formaldeh-yde condensation product of a compound which contains at least once the atomic grouping Example 1 22.8 parts of l-hydroxy-Z-aminobenzene-4-carboxylic acid phenylarnide are diazotized at '0" C. with the addition of 6.9 parts of sodium nitrite and 27 parts of hydrochloric acid of 30 per cent. strength, and the diazo com pound is coupled with 35.8 parts of 2-(4-aminobenzoyl)- arnino-S-hydroxynaphthaiene-7-sulfonic acid in a medium rendered alkaline with sodium carbonate.

The amino-monoazo-dyestufi is precipitated with sodium chloride, separated by filtration and pressed, and is then stirred in 400 parts of water with the addition of 7 parts of sodium nitrite and the resulting suspension is cooled to C. The whole is then mixed with 30 parts of hydrochloric acid of 30 per cent. strength and stirred for about 2 hours. The resulting diazo compound is mixed with a solution of 14.5 parts of S-hydroxyqui-noline and 12 parts of hydrochloric acid of 30 per cent. strength in 50 parts of water. 50 parts of sodium hydroxide solution of .30 per cent. strength are then added, and the whole is stirred for a few hours, then heated up to 65 C. 100 parts of sodium chloride are added in order to obtain the product in a well filterable form, and the precipitate is separated by filtration and dried.

There is obtained a dark brown powder soluble with a violet coloration in concentrated sulfuric acid and with a red coloration in dilute alkalies, which dyes cotton and regenerated cellulose by the single-bath or 2-bath after coppcring process red tints of very good fastness to washing and light. 7

Instead of 1 hydroxy 2 'u'ninobenzene 4 car boxylic acid phenylarnide there may be used as initial component i. hydroxy 2 aminobenezene 4 carboxylic acid (2'-chlorophenylamide), 1-hydroxy-2-an1inobcnzene-4-carboxylic acid naphthyl-(2)-amide or l-hyd'roay-Z-aminobenzene-4-carboxylic acid-,fi-hydroxyethylamide.

Example 2 ln 100 parts of turning sulfuric acid containing 24 per cent. of tree S03 there are introduced in portions, while stirring well, 51.6 parts of Z-nitro-l-hydroxybenzenel-carboxylic acid phenylamide. external cooling to prevent the temperature rising above 25? C. When the addition is complete, the whole is stirred for a further 30 minutes and poured on to ice.

- Then, a quantity of sodium hydroxide solution is added sufiicient to give the reaction mixture a weakly acid reaction, and the product sulfonated in the phenylamide radical is separated by filtration. By reduction of the Bchamp-Brimmeyr method with iron and a small amount of acetic acid an almost colorless product is obtained which maybe recrystallized from alcohol of '70 per cent. strength.

308 parts of the :sulfonated and reduced product are diazotized indirectly by dissolving that amount of the product together with 5.5 parts of sodium carbonate in 1500 parts of water, mixing the whole with 6.9 parts of sodium nitrite, and running in 40 parts of hydrochloric acid of 30 per centpstrength and 200 parts of water at 05 C. After about .3 hours the diazotization is complete. For the purpose of coupling the diazo suspension is mixed with 35.8 parts of 2-(4-aminobenzoyl)-amino- S-hydroxy naphthalene-lsulfonic acid in a medium rendered alkaline with sodium carbonate.

The resulting monoazo-dyestufi is separated, d-iazotized and coupled with 8-hydroxyquinoline in the manner described in'the second paragraph of Example 1.

The new dyestufi dyes cotton and regenerated cellulose by the single bath or Z-bath after-coppering process somewhat purer tints than the dyestutf described in Example 1. In other respects its properties corresponds to those of the dyestutf of Example 1.

Example 3 sulfonic acid and 30 parts of sodium carbonate in 500 parts of water.

The amino-monoazo-dyestufi is precipitated with sodium chloride, separated by filtration and pressed, and is all] Care is taken. y

. or '2-hath after-.coppering' process yellowish red then diazot'ized in 400 parts of water with hydrochloric acid and sodium nitrite in known manner. The diazomono-azo-compound is then coupled with '8-hydroxyquinoline to form the disazo-dyestutf as described in the second paragraph of Example 1.

The separated and dried dyestufl is a dark brown powder which dissolves in water with a red coloration. It dyes cotton and regenerated cellulose by the single hath tints of very good fastness to light.

Example 4 24.2 parts of 1-hydroxy-2-aminobenzene-4 carboxylic acid-N-methyl-phenylamide.are converted in known manher with the addition of 6.9 parts of sodium nitrite and 27 par-ts of hydrochloric acid of 30 per cent. strength into the d-iazo compound, and the latter is coupled with 35.8 parts of 2-(4'-'aminobenzoyl")-amino-5-hydroxyn'aphathalene-7-sulfonic acid in a medium rendered alkaline with sodium carbonate.

After '12 hours, the dyestuif so obtained isprecipitated with sodium chloride, separated by filtration and thoroughly pressed. The filter residue is stirred in 700 parts of water with the addition of 7 parts of sodium nin-ite,

' and theresulting suspension is cooled to 5 C. There are then added 30 parts or hydrochloric acid of '30 per cent. strength and the whole is stirred for about 2 hours. The diazo compound so obtained is then mixed with a solution of 14.5 parts of .8-hydroxyquinoline and 12 parts of hydrochloric acid of 30 per cent. strength in 50 parts of water. 50 parts of. an ammonia solution of 20 per cent. strength are then run in, and the whole is stirred for a few hours longer. The mixture. is then heated up to C., parts of sodium chloride are added, and the precipitate is separated by filtration and dried.

Thereis obtaineda dark brown powder which dissolves amazes complex sodium-copper tartrate is added, the goods are worked for V: hour at about 80 C., and then rinsed with cold water. There is obtained a red dyeing of very good fastness to washing and light.

in dilute alkalies with a red coloration, and dyes cotton and regenerated cellulose by the single bath or 2-bath aftcr-coppering process red tints of very good fastness to washing and acid.

Example 5 5 What we claim is: 100 parts of cotton are enteredat 50 C. into a dye- The disazo dyestuff of the formula OH HO Ho1s NH-0C-N= 003 U bath containing in 4000 parts of water 2 parts of 2111- References Cited in the file of this patent hydrous sodium carbonate and 1 part of the dyestufl UNITED STATES PATENTS obtainable as described in the first and second paragraphs of Example 1. The temperature is slowly raised to the 2,353, 75 fl t Ju1y 1 1944 boil, 30 parts of crystalline sodium sulfate are added, and 20 2,387,987 Felix Oct. 30, 1945 dyeing is carried on for hour at about 95 C. The 2,411,646 Anderau Nov. 26, 1946 bath is then allowed to cool to about 70 C., 1 part of 2,467,621

Kaiser Apr. 19, 1949 

